CN101144001A - Liquid rheology modifier - Google Patents
Liquid rheology modifier Download PDFInfo
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- CN101144001A CN101144001A CNA2007101472870A CN200710147287A CN101144001A CN 101144001 A CN101144001 A CN 101144001A CN A2007101472870 A CNA2007101472870 A CN A2007101472870A CN 200710147287 A CN200710147287 A CN 200710147287A CN 101144001 A CN101144001 A CN 101144001A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/02—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by the reacting monomers or modifying agents during the preparation or modification of macromolecules
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—Sulfur-containing compounds
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/0045—Polymers chosen for their physico-chemical characteristics
- C04B2103/0053—Water-soluble polymers
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/46—Water-loss or fluid-loss reducers, hygroscopic or hydrophilic agents, water retention agents
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Abstract
The present invention provides a liquid rheology modifier containing compounds (A) and (B) selected from combination (1) of compound (A) selected from cationic surfactants and compound (B) selected from anionic aromatic compounds and combination (2) of compound (A) from cationic surfactants and compound (B) selected from brominated compounds; and dicarboxylic acid (C).
Description
Technical field
The present invention relates to liquid rheology modifier.
Background technology
In general, for the slip that constitutes by water and powder, in order to control rheology rerum natura such as viscosity, use following technology: regulate the ratio of water and powder or adjust agent etc. and change the dispersion of particles state or add the technology of water-absorbing polymer with control surplus water etc. by pH; And in the slip system, add the technology of water-soluble high-molecular compound with the viscosifying action that utilizes high molecular winding and produced.
In addition, the combination of also having developed compound (A) and compound (B) is to be selected from the compound (A) of cationic surfactant and to be selected from the combination of the compound (B) of anionic property aromatics from (1), (2) be selected from the compound (A) of cationic surfactant and be selected from the slip rheology modifier of the combination of selecting in the combination of compound (B) of brominated compound, its purpose is to obtain following slip: show sufficient viscosity by short period of time mixing when making slip, and material separation is resistive stable, even if contact than high situation or with water at the pigment body, proterties or composition are also stable, for the hydraulic powder delay of not condensing, the sclerosis rerum natura is excellent (TOHKEMY 2003-313536 number) also.In addition, also develop the rheology modifier cover agent (TOHKEMY 2004-189978 number) of having used these compound combinations.And the world discloses No. 2005/035686 brochure and also discloses the surfactant composition that contains 2 kinds of tensio-active agents and cation property copolymer.
Summary of the invention
The present invention relates to a kind of liquid rheology modifier, it contains the 1st water-soluble low-molecular compound (hereinafter referred to as compound (A)), 2nd water-soluble low-molecular compound (hereinafter referred to as compound (B)) and the dicarboxylic acid (C) different with compound (A), wherein, the combination of compound (A) and compound (B) is selected from following combination: (1) is selected from the compound (A) of cationic surfactant and is selected from the combination of the compound (B) of anionic property aromatics, (2) be selected from the compound (A) of cationic surfactant and be selected from the combination of the compound (B) of brominated compound.
In addition, the invention still further relates to a kind of liquid rheology modifier, it contains the 1st water-soluble low-molecular compound (hereinafter referred to as compound (A)), the 2nd water-soluble low-molecular compound (hereinafter referred to as compound (B)) different with compound (A) and the amphiphilic compound (D) with hydrophilic group and hydrophobic group (hereinafter referred to as compound (D)) except that compound (A) and compound (B), wherein, the viscosity of this properties-correcting agent under 20 ℃ is below the 5000mPas; The combination of compound (A) and compound (B) is selected from following combination: (1) is selected from the compound (A) of cationic surfactant and the combination of the compound (B) that is selected from the combination of the compound (B) of anionic property aromatics, compound (A) that (2) are selected from cationic surfactant and is selected from brominated compound; In following standard test (I), when stopping to stir, can be observed in solution and circle round;
Standard test (I): adding 0.1N potassium hydroxide aqueous solution 90mL, rheology modifier 10mL in the beaker of 200mL, is that the glass stick of 6mm stirred for 180 seconds with the speed of 4 circle/seconds with diameter then.
In addition, the invention still further relates to a kind of liquid rheology modifier, it contains the 1st water-soluble low-molecular compound (hereinafter referred to as compound (A)), 2nd water-soluble low-molecular compound (hereinafter referred to as compound (B)) and the dicarboxylic acid (C) different with compound (A), wherein, the combination of compound (A) and compound (B) is selected from following combination: (1) is selected from the compound (A) of cationic surfactant and is selected from the combination of the compound (B) of anionic property aromatics, (2) be selected from the compound (A) of cationic surfactant and be selected from the combination of the compound (B) of brominated compound; The viscosity of this liquid rheology modifier under 20 ℃ is below the 5000mPas; In by normal portland cement 400g and the synthetic slip of water 400g, add this liquid rheology modifier 16g and mix, just carried out mixed slip viscosity at 20 ℃ down for more than the 3000mPas.
In addition, the present invention relates to contain the slip of the rheology modifier of powder, water and the invention described above.
In addition, the present invention relates to above-mentioned any liquid rheology modifier and be used for the purposes that the liquid towards rheological is carried out modification.
Embodiment
The rheology modifier of prior art shows the modified effect of rheology with 2 compound in use in slip, and for for liquid and do not mention for the form of single formulation.From metering with add the viewpoint of the operability of operation etc., the rheology modifier that expectation has single formulation form, if but modulated the aqueous solution that contains 2 compounds of above-mentioned prior art merely, the rheology modifier that tackify is remarkable, operability is good could not be obtained.Though also considered the viscosity in aqueous solution of having assigned to reduce this tackify by other one-tenth, improve handle property aspect do not see the sufficient rheology modifier of tackify again when using.
The invention reside in provides the rheology modifier that itself has the good viscosity of operability and can keep the liquid and single formulation form of the modified effects such as tackify effect when adding in the slip etc.
According to the present invention, the rheology modifier of liquid and single formulation form can be provided, the operability of metering and interpolation operation etc. increases.
Though rheology modifier of the present invention is the form of single formulation, viscosity is low, for example rheology modifier is added in the aqueous solution like that, when adding in water or the slip, contains the viscosity increased of the solvent of rheology modifier and water.
Employed the 1st water-soluble low-molecular compound (hereinafter referred to as compound (A)) forms association body structures such as wire micella with the 2nd water-soluble low-molecular compound (hereinafter referred to as compound (B)) different with compound (A) in the rheology modifier of the present invention in as the composition of rheology modified object, by forming this structure, show rheology modified effect.
The 1st mode of rheology modifier of the present invention is to contain compound (A), compound (B) and dicarboxylic acid (C).
Employed dicarboxylic acid (C) is at the concentration height of compound (A) and compound (B) and in the less solution of water in the rheology modifier of the present invention, enter into compound (A) and structure organizer (B), increase thereby hinder by compound (A) and the viscosity that (B) caused, the result can think that the preceding rheology modifier of dilution is a low viscosity.If by solution (aqueous solution) dilution that contains water, then dicarboxylic acid (C) moves in the aqueous solvent from compound (A) and association body structure (B), and the rheology modifier after result's dilution forms by compound (A) and structure (B) and shows high viscosity.
Whether the rheology modifier of the present invention of the 1st mode is also indeterminate according to utilizing aqueous solvent to dilute the different reason of viscosity performance situation takes place, but thought to influence the distribution of dicarboxylic acid (C) at water and association body structure.And think because dicarboxylic acid (C) has 2 carboxyls, so dicarboxylic acid (C) can hinder structure in entering the association body structure time and form, and in when dilution, dissolving easily in water.
Preferably compound (A) and compound (B) form the association body structure in dilute aqueous solution, and the association body structure is preferably the wire micella.The existence of association body structure can be by utilizing polaroid streaming birefringence or dynamic viscoelastic wait and confirm.
In TOHKEMY 2003-313536 communique, TOHKEMY 2004-189978 number etc., though also formed the wire micella, but in the combination of employed therein anionic property compound and cationic compound, do not see the method for the modified effect of the effect of tackify again in the time of when improving the property handled, can keeping so-called the use.According to the 1st mode of the present invention, by the use dicarboxylic acid, the performance in the time of can having the lowering viscousity that contains 2 compound compositions (aqueous solution etc.) concurrently and keep use.And, when pH is high, can promote the dissolving of dicarboxylic acid, obtain higher visco-elasticity.In addition, can not become the aspect of hazardous substance (by the hazardous substance of fire service law regulation), preferably use wetting ability, high boiling dicarboxylic acid yet from the gained rheology modifier.That is, the present invention can under with an organic solvent situation not, realize reducing single dosage form composition viscosity, guarantee low-temperature stability, keep performance and non-dangerous goodsization.
The combination of compound (A) and compound (B) is so long as form association body structure such as wire micella and get final product, preferably have following character: in the viscosity with compound (A) is that the viscosity of the aqueous solution below the 100mPas and compound (B) is the aqueous solution below the 100mPas when mixing, and can make at least 2 times of arbitrary viscosity in aqueous solution height before its viscosity ratio is mixed.More preferably can make at least 5 times of its height, further be preferably up to few 10 times, more further be preferably up to few 100 times, be preferably up to few 500 times especially.Here, viscosity is with the Brookfield viscometer (numerical value of C rotor [being the No.3 rotor during No. mark], 1.5r.p.m～12r.p.m) measure under 20 ℃ condition.At this moment, above-mentioned viscosity behavior is as long as show under any one rotating speed of 1.5r.p.m～12r.p.m.In addition, mixing is with 50/50 weight ratio each aqueous solution to be mixed.The concentration of the aqueous solution of the aqueous solution of compound (A) and compound (B) preferably is 0.01～50 weight %.
Here, the water-soluble low-molecular compound is meant at room temperature, in water with unit molecule or formed the state of structures such as association body, micella, liquid crystal or their mix under the state of depositing not the compound that can be separated with water.Be meant mutually have the macroscopic size, and the zone (colloid chemistry, the 1st volume, the 1st edition, 89～90 pages, October 12 nineteen ninety-five distribution, the same people of Tokyo chemistry) of clearly having stipulated statistics physical quantitys such as temperature, pressure.The water-soluble low-molecular compound preferably has solubleness more than 25 ℃ of following 0.001mg with respect to the 100g glassware for drinking water.In addition, preferably has molecular weight below 2000.
As the material that is selected from cationic surfactant, preferred quaternary salt type cationic surfactant, as the cationic surfactant of quaternary salt type, preferably in structure, has at least 1 alkyl that contains the saturated or undersaturated straight or branched of 10～26 carbon atoms.For example, can list alkyl (carbonatoms is 10～26) leptodactyline, alkyl (carbonatoms is 10～26) pyridinium salt, alkyl (carbonatoms is 10～26) imidazoline salt, alkyl (carbonatoms is 10～26) dimethyl benzyl ammonium salt etc., can list cetyltrimethylammonium chloride particularly, cetrimonium bromide, octadecyl trimethyl ammonium chloride, octadecyl trimethyl ammonium bromide, chlorination tallow base trimethyl ammonium, bromination tallow base trimethyl ammonium, chlorination hydrogenated-tallow group trimethyl ammonium, bromination hydrogenated-tallow group trimethyl ammonium, chlorination hexadecyl ethyl Dimethyl Ammonium, chlorination octadecyl ethyl Dimethyl Ammonium, chlorination hexadecyl propyl-dimethyl ammonium, cetylpyridinium chloride, chlorination 1,1-dimethyl-2-hexadecyl tetrahydroglyoxaline, Zettyns etc. can also be also with above-mentioned substance more than 2 kinds.From the water-soluble and viewpoint tackify effect, be preferably cetyltrimethylammonium chloride, octadecyl trimethyl ammonium chloride, cetylpyridinium chloride etc. particularly.In addition, from the viewpoint of the temperature stability of tackify effect, preferred and with the different cationic surfactant of the carbonatoms of the abovementioned alkyl more than 2 kinds as compound (A).
Particularly, when rheology modifier of the present invention being applicable to concrete etc., because the reinforcement corrosion that salt damage caused or the viewpoint of concrete deterioration, preferred use does not contain the quaternary ammonium salt of halogen such as chlorine from preventing.
As the not chloride quaternary salt that waits halogen, can list ammonium salt or imidazoline salt etc., can list the cetyl trimethyl sulfate methyl ammonium particularly, hexadecyldimethyl benzyl ammonium ethylsulfuric acid ethyl ester ammonium, octadecyl trimethylammonium sulfate methyl ammonium, octadecyl dimethyl ethyl sulfovinic acid ammonium, tallow base trimethylammonium sulfate methyl ammonium, tallow base dimethyl ethyl sulfovinic acid ammonium, 1,1-dimethyl-2-hexadecyl tetrahydroglyoxaline methyl sulfate, hexadecyldimethyl benzyl ammonium hydroxyethyl acetic ester ammonium, octadecyl dimethyl hydroxyethyl acetic ester ammonium, hexadecyldimethyl benzyl ammonium hydroxyethyl propionic ester ammonium, octadecyl dimethyl hydroxyethyl propionic ester ammonium, tallow base dimethyl hydroxyethyl acetic ester ammonium, tallow base dimethyl hydroxyethyl propionic ester ammonium etc.The not chloride quaternary ammonium salt of halogen that waits for example can obtain tertiary amine seasonization by methyl-sulfate, ethyl sulfate.
As the material that is selected from the anionic property aromatics, can list carboxylic acid and salt, phosphonic acids and salt thereof, sulfonic acid and salt thereof with aromatic nucleus, Whitfield's ointment, tosic acid, sulphosalicylic acid, phenylformic acid, a sulfosalicylic acid are specifically arranged, to sulfosalicylic acid, 4-sulfosalicylic phthalate, 5-sulfoisophthalic acid, right-sulfocarbolic acid, m-xylene-4-sulfonic acid, isopropyl sulfonic acid, cresotinic acid, styrene sulfonic acid, chlorinated benzene formic acid etc., these materials can form salt, can also be also with more than 2 kinds.When being polymkeric substance, preferable weight-average molecular weight (example gel permeation chromatography/polyoxyethylene converts) is less than 500.
Material as being selected from brominated compound is preferably inorganic salt, can list Sodium Bromide, Potassium Bromide, hydrogen bromide etc.
Among the present invention, compound (A) and compound (B) are also very low in denseer aqueous solution medium viscosity even if easily form association body person, in addition, even if the effective constituent concentration of the rheology modifier of aqueous phase is very low, also can show excellent rheology modified effect, the operability during from interpolation also is preferred.Among the present invention, can reach the tackify of effective constituent concentration under the utmost point few additive below the 10 weight %, and, even if in the very high slip system of ionic strength, also can show same effect, by the slip system, show the resistive highly stable such use of material separation when particularly the contacting tackifier rheological characteristics that can't obtain in the past with water.This is useful especially in containing the slip of hydraulic powder.
In addition, special preferred compound (A) is that alkyl (carbonatoms is 10～26) leptodactyline, compound (B) are the combination with sulfonate of aromatic nucleus, and slip also can show effect in the effective constituent concentration of aqueous phase below 5 weight %.Particularly, when being used for the slip of hydraulic powder, from the viewpoint that can not cause that at them sclerosis postpones, as compound (B), preferred toluenesulphonic acids, xylene monosulfonic acid, isopropyl sulfonic acid, styrene sulfonic acid or their salt, preferred especially tosic acid or its salt.
The preferred carbonatoms of dicarboxylic acid (C) is 3～10, and more preferably the carbonatoms between the carbon atom of 2 carboxyls is 0～8.Specifically can list and be selected from 2,4-diethyl glutarate, pimelic acid, nonane diacid, 4-methylcyclohexane-1,2-dicarboxylic acid, 4-methylcyclohexane-1,2-dicarboxylic acid, propanedioic acid, pentanedioic acid, 1,4-cyclohexane dicarboxylic acid, 1,2-cyclohexane dicarboxylic acid, norbornene dicarboxylic acids, toxilic acid, methylene-succinic acid, citraconic acid, tetrahydrobenzene-1,2-dicarboxylic acid, 2,2-dimethylated pentanedioic acid, 3, at least a kind of compound in 3-dimethylated pentanedioic acid, the 3-methyl hexanodioic acid.Content from rheology modifier and the viewpoint of separating out, more preferably be selected from 2, the 4-diethyl glutarate, pimelic acid, nonane diacid, pentanedioic acid, 4-methylcyclohexane-1,2-dicarboxylic acid and 4-tetrahydrotoluene-1, the 2-dicarboxylic acid, dimethylated pentanedioic acid, at least a kind of compound in the 3-methyl hexanodioic acid, from reducing the viewpoint of viscosity effectively with addition still less, be preferably 2, the 4-diethyl glutarate, nonane diacid, pentanedioic acid, 4-methylcyclohexane-1, the 2-dicarboxylic acid, 2, the 2-dimethylated pentanedioic acid, 3, the 3-dimethylated pentanedioic acid, 3-methyl hexanodioic acid.These dicarboxylic acid can also use acid anhydrides.
In addition, rheology modifier of the present invention preferably contains monocarboxylic acid (E).Contain the viscosity under viscosity, the particularly low temperature that monocarboxylic rheology modifier shows the aqueous solution in when dilution or slip rapidly.Contain in the monocarboxylic rheology modifier, because dicarboxylic acid and monocarboxylic wetting ability difference move in the aqueous solvent from the association body structure by the time difference, thereby more evenly, promptly show high viscosity.
The preferred carbonatoms of monocarboxylic acid (E) is 1～26, and from showing the viewpoint of higher slip viscosity, more preferably carbonatoms is 6～18, and from the viewpoint of product stability, further preferred carbonatoms is 6～12.In addition, preferred straight chain, saturated compound.Specifically can list and be selected from (E1) acetate, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid, capric acid, undecanoic acid, dodecylic acid, tridecanoic acid, tetradecanoic acid, pentadecylic acid, hexadecanoic acid, margaric acid, octadecanoic acid, nondecylic acid, arachic acid, heneicosanoic acid, docosoic acid, tricosanic acid, Lignoceric acid, pentacosoic acid, straight chain saturated monocarboxylic acids such as hexacosanoic acid, (E2) undecylenic acid, linolenic acid, linolic acid, oleic acid, straight chain unsaturated monocarboxylic acids such as elaidic acid, (E3) isovaleric acid, 2 ethyl hexanoic acid, 3,5, the 5-tri-methyl hexanoic acid, different palmitinic acid, side chain saturated monocarboxylic acids such as Unimac 5680, (E4) side chain unsaturated monocarboxylic acid, (E5) cholic acid, Septochol, gallodesoxycholic acid, bile acides such as lithocholic acid, phenoxy acetic acid, the compound more than at least a kind in the phenylglycollic acid etc.Wherein, cited compound group in preferred (E1), more preferably caproic acid, enanthic acid, sad, n-nonanoic acid, capric acid, undecanoic acid, dodecylic acid.The form of the salt that these monocarboxylic acids can also be neutralized with a part is used.
The content of monocarboxylic acid (E) with respect to the compound (A) of 100 weight parts be preferably 0.7～70 weight part, more preferably 2～30 weight parts, most preferably be 3～20 weight parts.
Rheology modifier of the present invention is preferably stopping to can be observed in solution when stirring in following standard test (I) circling round.In addition, rheology modifier of the present invention is preferably stopping to can be observed in solution when stirring in following standard test (II) circling round.All can be observed in solution when more preferably stopping to stir and circle round in following standard test (I) with (II).Here said circling round is meant association body generation complexing in the solution, has the meaning of elastic property, is meant the state that the bubble that circles round in solution moves to the direction opposite with sense of rotation when stopping to stir.By inference, circle round, therefore in the mixed solution of potassium hydroxide aqueous solution and rheology modifier, formed association body structures such as wire micella by compound (A) and compound (B) owing to produced.
Standard test (I): adding 0.1N potassium hydroxide aqueous solution 90mL, rheology modifier 10mL in the 200mL beaker, is that the glass stick of 6mm stirred for 180 seconds with the speed of 4 circle/seconds with diameter then.
Standard test (II): adding 0.1N potassium hydroxide aqueous solution 95mL, rheology modifier 5mL in the 200mL beaker, is that the glass stick of 6mm stirred for 180 seconds with the speed of 4 circle/seconds with diameter then.
Among above-mentioned standard test (I), (II), the glass stick of stirring all is to put into to the bottom, and rotation is all carried out along wall.Stop to stir the back visual observation, on the direction opposite, when mobile, then judge to have circling round of bubble with sense of rotation when observing bubble.
The 2nd mode of rheology modifier of the present invention is that to contain compound (A), compound (B) and the compound (D) except that compound (A) and compound (B) and the viscosity under 20 ℃ be liquid rheology modifier below the 5000mPas, in standard test (I), when stopping to stir, can be observed in solution and circle round.The standard test of circling round (I) is the test method identical with the 1st mode.
In the 2nd mode of rheology modifier of the present invention, compound (A) can use the compound identical with the 1st mode with compound (B).
For compound (D), the properties-correcting agent that contains compound (A) and compound (B) by contain this compound (D), preferably by in properties-correcting agent, containing 0.1～30 weight %, thereby the viscosity under 20 ℃ reaches below the 5000mPas.Usually, in compound of the present invention (A) and compound (B), add entry and can not realize this viscosity.Therefore, water is not equivalent to compound (D).In addition, compound (D) preferably is dissolved in the compound in the mixing solutions of compound (A) and compound (B).As compound (D), be preferably amphiphilic compound with hydrophilic group and hydrophobic group, be preferably compound with ionic functional group.Here, ionic functional group comprises that the carboxyl of carboxylic acid, the amino of amine etc. can become the group of alkali type or acid type.Wherein can list the carboxylic acid compound of dicarboxylic acid, tricarboxylic acid, tetracarboxylic acid and so on and the compound of sulfonic acid class etc., specifically, except the compound of enumerating as dicarboxylic acid (C), can also list hexane-1,3, tricarboxylic acids such as 6-tricarboxylic acid, dicarboxylic esters such as adipate monoester etc.From the viewpoint of the viscosity of rheology modifier, the molecular weight of compound (D) is preferably below 1000, more preferably below 500.In addition, from the viewpoint of the operability of the storage stability of rheology modifier and interpolation, compound (D) is preferably the compound that is dissolved in the aqueous solution that contains compound (A) and compound (B).The viewpoint of the rheology modified effect during from interpolation to rheology modified object, compound (D) preferably is dissolved in the water under the pH of rheology modified object.
The 2nd mode of rheology modifier of the present invention is: in by normal portland cement 400g and the synthetic slip of water 400g, add this rheology modifier 16g and mix, just mixed the back, preferably mix 60 seconds with interior slip viscosity preferably be down more than the 3000mPas at 20 ℃, more preferably more than the 3500Pas, more preferably more than the 4000Pas.
The 3rd mode of rheology modifier of the present invention for contain compound (A), compound (B) and dicarboxylic acid (C) and the viscosity under 20 ℃ be below the 5000mPas, be preferably below the 3000mPas, the liquid rheology modifier below the 2000mPas more preferably, in by normal portland cement 400g and the synthetic slip of water 400g, add this rheology modifier 16g and mix, just mixed the back, preferably mix 60 seconds with interior slip viscosity be more than the 3000mPas down at 20 ℃, be preferably more than the 3500Pas, more preferably more than the 4000Pas.
In the 3rd mode of rheology modifier of the present invention, compound (A), compound (B) and dicarboxylic acid (C) can use the compound identical with the 1st mode.
In addition, in the 3rd mode of rheology modifier of the present invention, preferably contain monocarboxylic acid (E).Monocarboxylic acid (E) can use the compound identical with the 1st mode.
And then, in the 3rd mode of rheology modifier of the present invention, preferably in standard test (I) and/or standard test (II), stopping to can be observed in solution when stirring and circling round.The standard test of circling round (I), (II) are the test method identical with the 1st mode.
In arbitrary mode, need only the performance that does not hinder this properties-correcting agent in the rheology modifier of the present invention, then other composition be can contain, dispersion agent, AE agent, delayed-action activator, fast hard agent, promotor, air bubble agent, whipping agent, defoamer, rust-preventive agent, tinting material, mould inhibitor, crackle minimizing agent, swelling agent, dyestuff, pigment etc. for example can be contained.
The mol ratio of compound in the rheology modifier of the present invention (A) and compound (B) (effective constituent mol ratio) is different according to the combination of compound (A) and compound (B), higher regional different of tackify effect, as long as suitably determine according to target tackify degree, from the viewpoint of gained viscosity and association shape, compound (A)/compound (B)=1/20～20/1, be preferably 1/20～4/1, more preferably 1/3～2/1, be preferably 1/1～2/3 especially.
The content of compound (A) in rheology modifier preferably contains with the concentration of separating out less than generation, from the viewpoint of the viscosity that reduces rheology modifier, compound in rheology modifier (A) preferably contains 2.5～40 weight %, more preferably 5～30 weight %, 10～20 weight % more preferably.
The content of compound (B) in rheology modifier preferably contains with the concentration of separating out less than generation, from the viewpoint of the viscosity that reduces rheology modifier, compound in rheology modifier (B) preferably contains 1.5～30 weight %, more preferably 3～20 weight %, 5～15 weight % more preferably.
Dicarboxylic acid (C) or the content of compound (D) in rheology modifier preferably contain with the concentration of separating out less than generation, from the viewpoint of the viscosity that reduces rheology modifier, dicarboxylic acid in rheology modifier (C) or compound (D) preferably contain 0.1～30 weight %, more preferably 0.3～15 weight %, 0.5～10 weight % more preferably.
In addition, content in the rheology modifier when containing monocarboxylic acid (E) preferably contains with the concentration of separating out less than generation, from reducing the viewpoint show rheology modified effect at short notice, monocarboxylic acid in rheology modifier (E) preferably contains 0.1～5 weight %, more preferably 0.3～3 weight %, 0.5～2 weight % more preferably.
In addition, the weight ratio of the dicarboxylic acid (C) in the rheology modifier of the present invention and compound (A) and compound (B) total amount is preferably (C)/[(A)+(B)]=0.1/100～120/100, more preferably 1/100～80/100, more preferably 4/100～60/100.And then when containing monocarboxylic acid (E), the weight ratio of dicarboxylic acid (C) and monocarboxylic acid (E) is preferably (C)/(E)=100/100～100/1, more preferably 100/70～100/10, more preferably 100/50～100/5.
The weight ratio of the compound in the rheology modifier of the present invention (D) and compound (A) and compound (B) total amount is preferably (D)/[(A)+(B)]=0.1/100～120/100, more preferably 1/100～80/100, more preferably 4/100～60/100.
Rheology modifier of the present invention is liquid, is preferably the aqueous solution.From in order to become liquid viewpoint, the content of the water in the rheology modifier is preferably 50 weight % above, more preferably 50～80 weight %, 60～70 weight % more preferably.The total content of compound (A), compound (B) and dicarboxylic acid (C) or compound (D) preferably in rheology modifier is below the 50 weight %, more preferably 50～20 weight %, 40～25 weight % more preferably.From making the uniform viewpoint of the addition of rheology modified object, compound (A), compound (B), dicarboxylic acid (C) and compound (D) are not all preferably separated out in rheology modifier.And when containing monocarboxylic acid (E), preferred compound (A), compound (B), dicarboxylic acid (C) and monocarboxylic acid (E) are not all separated out in rheology modifier.
In the rheology modifier of the present invention, to obtain higher viscoelastic aspect, the pH of preferred slip is more than 7 under at least one temperature of 0 ℃～60 ℃ from the diffusion that can promote dicarboxylic acid (C) or compound (D).
In addition, the viscosity of rheology modifier of the present invention is from the viewpoint of operability, preferably 20 ℃ down for below the 10000mPas, more preferably below the 5000mPas, more preferably below the 3000mPas, below the 2000mPas.Particularly, the viscosity of rheology modifier of the present invention under 20 ℃ of the 2nd mode be preferably below the 5000mPas, more preferably below the 3000mPas, more preferably below the 2000mPas.In addition, preferably, in the rheology modifier of the present invention of the 1st mode, viscosity under 20 ℃ be below the 5000mPas so that for below the 3000mPas, again and then be rheology modifier below the 2000mPas, in by normal portland cement 400g and the synthetic slip of water 400g, add this rheology modifier 16g and mix, just mixed the back, preferably mix 60 seconds with interior slip viscosity preferably be down more than the 3000mPas at 20 ℃, more preferably more than the 3500Pas, more preferably more than the 4000Pas.
In addition, even if because rheology modifier of the present invention also can be given good rheological characteristics in the high slip system of ionic strength, use in the slip of the scope that therefore preferred specific conductivity at water is the scope of the scope of 0.01～80mS/cm, preferred 0.1～60mS/cm, preferred especially 1～40mS/cm.Particularly preferably in using in the higher slip system of the specific conductivity of the water that contains hydraulic-compositions such as cement.
According to the present invention, can obtain to contain the slip of the rheology modifier of the invention described above, particularly contain the slip of rheology modifier, hydraulic powder and the water of the invention described above.
Rheology modifier of the present invention can preferably be applicable to the pigment body than being in 30～600% the slip, more preferably is applicable to the pigment body than being in 30～300% the slip.Powder during as this slip of manufacturing can use to have the hydraulic powder that the hardened rerum natura takes place by hydration reaction.For example, can list cement and gypsum.In addition, can also use filler, for example lime carbonate, flying dust, blast-furnace slag, silicon ash, wilkinite, clay (with the hydrated aluminium silicate is the natural mineral of principal constituent: kaolin, halloysite etc.).These powders can use separately, can also mix use.And, can also in these powders, add sand, gravel and their mixture as required as aggregate.In addition, can also be useful in the slip or soil of the inorganic oxide class powders except that above-mentioned such as titanium oxide.
In addition, in rheology modifier of the present invention, effective constituent concentration in the slip can suitably determine according to target tackify degree, by method to such as rheology modifier of the present invention being added in the synthetic in advance slip, when making slip, add, can obtain to contain the slip of properties-correcting agent of the present invention.When for the combination in the combination that is selected from compound (A) that (1) be selected from cationic surfactant and the compound (B) that is selected from the anionic property aromatics, compound (A) that (2) are selected from cationic surfactant and the compound (B) that is selected from brominated compound, total effective constituent of compound (A) and compound (B) according to be preferably with effective constituent densitometer at the slip aqueous phase 0.01～20 weight %, more preferably 0.1～15 weight %, more preferably 0.1～10 weight %, the mode that is preferably 3～10 weight % are especially used.
From the viewpoint of rheology modified effect, contain the slip of rheology modifier of the present invention, particularly contain hydraulic powder hydraulicity slip viscosity preferably at 20 ℃ down for more than the 1000mPas, more preferably more than the 2000mPas.
The hydraulicity slip that contains rheology modifier of the present invention also can contain dispersion agent.In the dispersion agent, as water reducer, can list ligninsulfonate and derivative thereof, the oxidation carboxylate salt, many alcohol derivate, as high-performance water reducing agent and high-performance AE water reducer, (Kao Corp produces: マ イ テ イ 150) can to list naphthalene system, (Kao Corp produces the melamine class: マ イ テ イ 150V-2), (Kao Corp produces polycarboxylic acid: マ イ テ イ 3000, NMB company produces: レ is PVC Le De SP, Japan's catalyst Co. production: ア Network ア ロ Star Network FC600, ア Network ア ロ Star Network FC900), as cationic surfactant, (Kao Corp produces: Port イ ズ シ リ-ズ) etc. can to list the polyocarboxy acid type tensio-active agent.Wherein, flowability and the aspect of viscosity, preferably polycarboxylic acid high-performance water reducer and the polyocarboxy acid type tensio-active agent from taking into account slip.
The dispersant that contains in the hydraulicity slip of rheology modifier of the present invention is preferably 0.01～5 weight %, 0.05～3 weight % more preferably with respect to hydraulic powder usually in effective constituent.
Rheology modifier of the present invention is except compound of the present invention (A), compound (B), dicarboxylic acid (C) and compound (D), when further containing monocarboxylic acid (E), except monocarboxylic acid (E), can also use other known water-soluble polymer.As other known water-soluble polymer, for example can list derivatived cellulose, polyacrylic acid based polymer, polyoxyethylene glycol, polyvinyl alcohol, rubber is polyose, microbial fermentation polyose, cation property copolymer etc.
As cation property copolymer, preferably contain cationic nitrogen, more preferably on the cationic nitrogen of this cation property copolymer bonding to have that to be selected from carbonatoms be 1～22 alkyl, contain carbonatoms be group in 2～8 the oxyalkylene group polyoxyalkylenes, hydrogen atom and the acryloxyalkyl that form.As the object lesson of cation property copolymer, can list polyene propyl group trialkyl ammonium salts, poly-(diallyl dimethyl ammonium salt), poly-(methacryloxyethyl dimethyl ethyl ammonium salt), PMAm oxypropyl trimethyl ammonium salt, cationic starch, Poise C-80M, cationization Natvosols etc. such as polyene oxypropyl trimethyl ammonium salt.Wherein, be preferably selected from cation property copolymer in poly-(diallyl dimethyl ammonium salt), polymethyl acyloxy ethyl dimethyl ethyl ammonium salt, PMAm oxypropyl trimethyl ammonium salt, methacryloxyethyl dimethyl ethyl ammonium salt-vinylpyrrolidone copolymer and the Methacrylamide oxypropyl trimethyl ammonium salt-vinylpyrrolidone copolymer.In addition, from the viewpoint of rheology modified effect, be the alkylsurfuric acid ion preferably to ion, more preferably sulfovinate, Methylsulfate.The molecular weight of cation property copolymer is preferably more than 1000, and more preferably 100～3,000,000.This molecular weight is the weight-average molecular weight of measuring under the following conditions by gel permeation chromatography.
Chromatographic column: α-M (East ソ-production) 2 connections
Elutriant: 0.15mol/L sodium sulfate, 1% aqueous acetic acid
Flow velocity: 1.0mL/min
Temperature: 40 ℃
Detector: RI
Molecular weight standard uses pulullan polysaccharide (pullulan)
The content of cation property copolymer is preferably 0.1～30 weight %, 1～20 weight % more preferably in rheology modifier of the present invention.In addition, the weight ratio of cationic surfactant and cation property copolymer is: preferred cationic polymkeric substance/cationic surfactant=1/100～200/100, more preferably 5/100～130/100.
Contain the hydraulicity slip of rheology modifier of the present invention as long as do not hinder the performance of host, can also contain other composition, for example AE agent, delayed-action activator, fast hard agent, promotor, air bubble agent, whipping agent, defoamer, crackle reduce agent, swelling agent etc.
To contain the hardening composition that the slip sclerosis of rheology modifier of the present invention and hydraulic powder forms and compare with the situation of using water-soluble polymer, initial stage sclerosis rerum natura is more excellent.And, can in containing the hydraulicity slip of rheology modifier of the present invention, modulate hydraulic-composition by combined aggregate.The hardening composition that the sclerosis of this hydraulic-composition forms is compared with the situation of using water-soluble polymer, and initial stage sclerosis rerum natura is more excellent, is particularly suitable in the works etc.
The blended aggregate can use fine aggregate or coarse aggregate in containing the hydraulicity slip of rheology modifier of the present invention, be not particularly limited, but the preferred aggregate that water-intake rate is low, aggregate intensity is high.As coarse aggregate, can list rivers and creeks, land, mountain, sea, lime gravel, their rubble, blast-furnace slag coarse aggregate, Rhometal slag coarse aggregate, lightweight coarse aggregate (artificial and natural) and regenerated coarse aggregate etc.As fine aggregate, can list rivers and creeks, land, mountain, sea, lime sand, silica sand and their broken sand, blast-furnace slag fine aggregate, Rhometal slag fine aggregate, lightweight fine aggregate (artificial and natural) and recycled fine aggregate etc.
The slip that contains liquid rheology modifier of the present invention can contain hydraulic powder, and the slip that contains this rheology modifier hardens under the situation of the hydration reaction that can not hinder hydraulic powder.From then on viewpoint is set out, and can be suitable in building and the construction applications.
Embodiment
Following embodiment describes enforcement of the present invention.Embodiment describes example of the present invention, and is not used in qualification the present invention.
＜embodiment 1 〉
(1) modulation of rheology modifier and viscosity, the mensuration of circling round
With the liquid rheology modifier of the modulation of the composition shown in the table 1.Utilize Water Tank with Temp.-controlled to adjust to 20 ℃, use Brookfield viscometer (No.3 rotor, 12rpm) to measure viscosity.In addition, circle round by the method observation of standard test (I).The results are shown in the table 2.
In addition, the viscosity (Brookfield viscometer (No.3 rotor, 12rpm)) of the paratoluenesulfonic acid sodium salt 0.8 weight % aqueous solution under 20 ℃ is below the 100mPas, and the viscosity of the 1.3 weight % aqueous solution under 20 ℃ of cetyltrimethylammonium chloride/octadecyl trimethyl ammonium chloride mixture (weight ratio 1/1) is below the 100mPas.Viscosity in aqueous solution when mixing these aqueous solution with 50/50 weight ratio is 1100mPas.
(2) the rheology modified evaluation of hydraulicity slip
After utilizing cake normal portland cement 400g, water 400g to be mixed for 30 seconds with hand mixer, liquid rheology modifier (the X=3.0 weight % that adds table 1, but when X=3.0 viscosity surpasses 10000Pas, X=5.0 weight %, when X=5.0 viscosity surpasses 10000mPas, X=10.0 weight %) 16g, 60 seconds of remix.Utilize Viscotester (リ オ Application produce VT-04E) measure the viscosity of synthetic slip.Reach the temperature that 20 ℃ mode is modulated material according to slurry temperature.The results are shown in the table 2.
Table 1
| Kind | Weight % | |
| Compound (A) | Cetyltrimethylammonium chloride/octadecyl trimethyl ammonium chloride=50/50 (weight ratio) | 14.5 |
| Compound (B) | Paratoluenesulfonic acid sodium salt | 10.0 |
| Dicarboxylic acid (C) | The compound of table 2 | X * |
| Other | Water | Remainder |
| Amount to | 100.0 | |
*X is the weight % shown in the table 2.
Table 2
| Dicarboxylic acid or monocarboxylic acid | The viscosity of rheology modifier (mPas/20 ℃) | Hydraulicity slip viscosity (mPas/20 ℃) | The observation that standard test (I) is circled round | |||
| Kind | X=3 weight % | X=5 weight % | X=10 weight % | |||
| The present invention's product | Propanedioic acid | Surpass 10000 | Surpass 10000 | 4600 | 4800 | Circle round |
| Pentanedioic acid | 10000 | 2000 | 200 | 4800 | Circle round | |
| Pimelic acid | 500 | 150 | - | 4300 | Circle round | |
| Nonane diacid | 500 | - | - | 4100 | Circle round | |
| 1, the 4-cyclohexane diacid | 900 | 150 | - | 4200 | Circle round | |
| 1,2-cyclohexane diacid (tetrahydrophthalic acid) | 500 | - | - | 4600 | Circle round | |
| 4-methylcyclohexane-1, the 2-dicarboxylic acid | 350 | - | - | 4500 | Circle round | |
| 2, the 4-diethyl glutarate | 200 | 150 | - | 4800 | Circle round | |
| Norbornene dicarboxylic acids | 2000 | 900 | - | 4300 | Circle round | |
| Toxilic acid | 10000 | 10000 | 900 | 4800 | Circle round | |
| Methylene-succinic acid | 8950 | 1100 | 150 | 4500 | Circle round | |
| Citraconic acid | 10000 | 1800 | 100 | 4700 | Circle round | |
| Tetrahydrobenzene-1, the 2-dicarboxylic acid | 750 | 150 | - | 4300 | Circle round | |
| 4-tetrahydrotoluene-1, the 2-dicarboxylic acid | 600 | - | - | 4500 | Circle round | |
| Product relatively | N-nonanoic acid | Emulsification, layering | Emulsification, layering | Emulsification, layering | - | - |
| Caproic acid | Emulsification, layering | Emulsification, layering | Emulsification, layering | - | - | |
| Do not have (blank) | Surpass 100000 | - | - | 5000 | Circle round | |
＜embodiment 2 〉
According to the liquid rheology modifier of the modulation of the composition shown in the table 3.Utilize Water Tank with Temp.-controlled to adjust to 20 ℃, use Brookfield viscometer (No.3 rotor, 12rpm) to measure viscosity.The results are shown in the table 4.In addition, the rheology modifier of table 4 has all been observed in standard test (I) and has been circled round.
(1) the rheology modified evaluation of hydraulicity slip
After utilizing cake with hand mixer normal portland cement 400g, water 400g to be mixed for 30 seconds, the liquid rheology modifier 16g of adding table 3 also mixed for 60 seconds.This slip in mixing of visual observation, with viscosity no longer rise reach capacity second number as noting time of arrival.After the mixing, utilize Viscotester (リ オ Application is produced VT-04E) to measure the viscosity of slip.Even if when mix 60 seconds viscosity rise and also not reach when stablize, mix with end in 60 seconds.The mode that reaches 10 ℃ or 20 ℃ according to slurry temperature is adjusted the temperature of material.The results are shown in the table 4.
Table 3
| Kind | Weight % | |
| Compound (A) | Cetyltrimethylammonium chloride/octadecyl trimethyl ammonium chloride=50/50 (weight ratio) | 14.5 |
| Compound (B) | Paratoluenesulfonic acid sodium salt | 10.0 |
| Dicarboxylic acid (C) | The compound of table 4 | X * |
| Monocarboxylic acid (E) | The compound of table 4 | Y * |
| Other | Water | Remainder |
| Amount to | 100.0 | |
*X, Y are the weight % shown in the table 4.
Table 4
| No. | Dicarboxylic acid | Monocarboxylic acid | The viscosity of rheology modifier (mPas/20 ℃) | Circle round | Test temperature (20 ℃) | Test temperature (10 ℃) | |||||
| Kind | X (weight %) | Kind | Y (weight %) | Standard test (I) | Standard test (II) | Time of arrival (second) | Hydraulicity slip viscosity (mPas/20 ℃) | Time of arrival (second) | Hydraulicity slip viscosity (mPas/10 ℃) | ||
| 2-1 | Pentanedioic acid | 10.0 | Caproic acid | 0.00 | 200 | Have | Have | 30 | 4500 | Surpass 60 | 3100 |
| 2-2 | Pentanedioic acid | 10.0 | Caproic acid | 0.50 | 230 | Have | Have | 20 | 5200 | 45 | 3900 |
| 2-3 | Pentanedioic acid | 10.0 | Caproic acid | 1.00 | 220 | Have | Have | 15 | 5600 | 30 | 4500 |
| 2-4 | Pentanedioic acid | 10.0 | Caproic acid | 2.00 | 195 | Do not have | Have | 10 | 6000 | 5 | 6000 |
| 2-5 | Pentanedioic acid | 10.0 | Capric acid | 0.00 | 200 | Have | Have | 30 | 4500 | Surpass 60 | 3100 |
| 2-6 | Pentanedioic acid | 10.0 | Capric acid | 0.25 | 350 | Have | Have | 30 | 4800 | 50 | 3400 |
| 2-7 | Pentanedioic acid | 10.0 | Capric acid | 0.50 | 410 | Have | Have | 20 | 5200 | 30 | 3100 |
| 2-8 | Pentanedioic acid | 10.0 | Capric acid | 0.75 | 475 | Have | Have | 10 | 5500 | 16 | 4700 |
| 2-9 | Pentanedioic acid | 10.0 | Capric acid | 1.00 | 530 | Have | Have | 7 | 6000 | 7 | 5000 |
| 2-10 | Pentanedioic acid | 10.0 | Capric acid | 1.50 | 550 | Do not have | Have | 7 | 5500 | 5 | 5000 |
| 2-11 | Pentanedioic acid | 10.0 | Capric acid | 2.00 | 450 | Have | Have | 7 | 5200 | 5 | 5000 |
| 2-12 | Pentanedioic acid | 10.0 | Oleic acid | 0.00 | 200 | Have | Have | 30 | 4500 | Surpass 60 | 3100 |
| 2-13 | Pentanedioic acid | 10.0 | Oleic acid | 0.50 | 390 | Have | Have | 20 | 4500 | 30 | 4800 |
| 2-14 | Pentanedioic acid | 10.0 | Oleic acid | 1.00 | 500 | Have | Have | 18 | 4500 | 10 | 6500 |
| 2-15 | Pentanedioic acid | 10.0 | Oleic acid | 1.50 | 400 | Do not have | Have | 6 | 600 | 10 | 950 |
| 2-16 | Nonane diacid | 3.0 | 2 ethyl hexanoic acid | 0.00 | 500 | Have | Have | 30 | 4700 | Surpass 60 | 1300 |
| 2-17 | Nonane diacid | 3.0 | 2 ethyl hexanoic acid | 1.00 | 250 | Have | Have | 10 | 2200 | 25 | 4500 |
| 2-18 | Diethyl glutarate | 3.0 | N-nonanoic acid | 0.00 | 200 | Have | Have | 30 | 4500 | Surpass 60 | 1000 |
| 2-19 | Diethyl glutarate | 3.0 | N-nonanoic acid | 1.00 | 165 | Have | Have | 10 | 8000 | 7 | 6000 |
| 2-20 | Pimelic acid | 5.0 | Enanthic acid | 0.00 | 150 | Have | Have | 30 | 4800 | Surpass 60 | 1600 |
| 2-21 | Pimelic acid | 5.0 | Enanthic acid | 1.00 | 350 | Have | Have | 10 | 5500 | 10 | 4800 |
| 2-22 | 1, the 4-cyclohexane diacid | 5.0 | Undecanoic acid | 0.00 | 600 | Have | Have | 30 | 4600 | Surpass 60 | 900 |
| 2-23 | 1.4-cyclohexane diacid | 5.0 | Undecanoic acid | 1.00 | 205 | Have | Have | 6 | 9000 | 9 | 4600 |
| 2-24 | Methyl cyclohexane diacid | 3.0 | Dodecylic acid | 0.00 | 350 | Have | Have | 40 | 4700 | Surpass 60 | 1600 |
| 2-25 | Methyl cyclohexane diacid | 3.0 | Dodecylic acid | 1.00 | 295 | Have | Have | 10 | 6200 | 40 | 3000 |
| 2-26 | Methyl cyclohexane diacid | 3.0 | Undecanoic acid | 0.00 | 600 | Have | Have | 30 | 4500 | Surpass 60 | 1500 |
| 2-27 | Methyl cyclohexane diacid | 3.0 | Undecanoic acid | 1.00 | 235 | Have | Have | 10 | 6500 | 25 | 2000 |
| 2-28 | 1, the 2-cyclohexane diacid | 3.0 | Sad | 0.00 | 500 | Have | Have | 25 | 5200 | 60 | 1600 |
| 2-29 | 1, the 2-cyclohexane diacid | 3.0 | Sad | 1.00 | 200 | Have | Have | 12 | 6500 | 20 | 5500 |
| 2-30 | Tetrahydrobenzene-1, the 2-dicarboxylic acid | 5.0 | 3,5,5 Trimethylhexanoic acid | 0.00 | 150 | Have | Have | 25 | 4300 | Surpass 60 | 4000 |
| 2-31 | Tetrahydrobenzene-1, the 2-dicarboxylic acid | 5.0 | 3,5,5 Trimethylhexanoic acid | 1.00 | 150 | Have | Have | 10 | 5000 | 15 | 4700 |
| 2-32 | Methylene-succinic acid | 10.0 | Caproic acid | 0.00 | 150 | Have | Have | 15 | 5800 | 40 | 3000 |
| 2-33 | Methylene-succinic acid | 10.0 | Caproic acid | 1.00 | 175 | Have | Have | 6 | 6500 | 7 | 6000 |
| 2-34 | Citraconic acid | 10.0 | Enanthic acid | 0.00 | 100 | Have | Have | 12 | 6500 | 30 | 4000 |
| 2-35 | Citraconic acid | 10.0 | Enanthic acid | 1.00 | 215 | Have | Have | 7 | 6000 | 5 | 6000 |
| 2-36 | Pentanedioic acid | 10.0 | Capric acid | 0.00 | 120 | Have | Have | 10 | 6200 | 25 | 3900 |
| Nonane diacid | 1.0 | ||||||||||
| 2-37 | Pentanedioic acid | 10.0 | Capric acid | 1.00 | 225 | Have | Have | 8 | 6200 | 7 | 5000 |
| Nonane diacid | 1.0 |
＜embodiment 3 〉
According to the liquid rheology modifier of the modulation of the composition shown in the table 5, estimate similarly to Example 2.The results are shown in the table 6.In addition, the rheology modifier of table 6 has all been observed in standard test (I) and standard test (II) and has been circled round.
Table 5
| Kind | Weight % | |
| Compound (A) | Cetyltrimethylammonium chloride/octadecyl trimethyl ammonium chloride=50/50 (weight ratio) | 14.5 |
| Compound (B) | The m-xylene sodium sulfonate | 9.1 |
| Dicarboxylic acid (C) | The compound of table 6 | X * |
| Monocarboxylic acid (E) | The compound of table 6 | Y * |
| Other | Water | Remainder |
| Amount to | 100.0 | |
*X, Y are the weight % shown in the table 6.
Table 6
| No. | Dicarboxylic acid | Monocarboxylic acid | The viscosity of rheology modifier (20 ℃) | Test temperature (20 ℃) | Test temperature (10 ℃) | ||||
| Kind | X (weight %) | Kind | Y (weight %) | Time of arrival (second) | Hydraulicity slip viscosity (20 ℃) | Time of arrival (second) | Hydraulicity slip viscosity (10 ℃) | ||
| 3-1 | Pentanedioic acid | 10.0 | Capric acid | 1.00 | 470 mPa·s | 10 | 9500 mPa·s | 5 | 4800 mPa·s |
＜embodiment 4 〉
According to the liquid rheology modifier of the modulation of the composition shown in the table 7, estimate similarly to Example 2.The results are shown in the table 8.In addition, the rheology modifier of table 8 has all been observed in standard test (I) and standard test (II) and has been circled round.
Table 7
| Kind | Weight % | |
| Compound (A) | Palmityl trimethyl ammonium chloride/tetradecyl trimethyl ammonium chloride=87/13 (weight ratio) | 11.2 |
| Compound (B) | Paratoluenesulfonic acid sodium salt | 10.0 |
| Dicarboxylic acid (C) | The compound of table 8 | X * |
| Monocarboxylic acid (E) | The compound of table 8 | Y * |
| Other | Water | Remainder |
| Amount to | 100.0 | |
*X, Y are the weight % shown in the table 8.
Table 8
| No. | Dicarboxylic acid | Monocarboxylic acid | The viscosity of rheology modifier (20 ℃) | Test temperature (20 ℃) | Test temperature (10 ℃) | ||||
| Kind | X (weight %) | Kind | Y (weight %) | Time of arrival (second) | Hydraulicity slip viscosity (20 ℃) | Time of arrival (second) | Hydraulicity slip viscosity (10 ℃) | ||
| 4-1 | Pentanedioic acid | 10.0 | Capric acid | 1.00 | 215 | 7 | 6000 | 5 | 9000 |
＜embodiment 5 〉
According to the liquid rheology modifier of the modulation of the composition shown in the table 9, estimate similarly to Example 2.The results are shown in the table 10.
Table 9
| Kind | Weight % | |
| Compound (A) | Cetyltrimethylammonium chloride/octadecyl trimethyl ammonium chloride=50/50 (weight ratio) | 14.5 |
| Compound (B) | Paratoluenesulfonic acid sodium salt | 10.0 |
| Dicarboxylic acid (C) | The compound of table 10 | X * |
| Monocarboxylic acid (E) | The compound of table 10 | Y * |
| Cation property copolymer | Poly-(methacryloxyethyl dimethyl ethyl sulfovinic acid ammonium) (weight-average molecular weight 120,000) | 5.0 |
| Other | Water | Remainder |
| Amount to | 100.0 | |
*X, Y are the weight % shown in the table 10.
Table 10
| No. | Dicarboxylic acid | Monocarboxylic acid | The viscosity of rheology modifier (20 ℃) | Circle round | Test temperature (20 ℃) | Test temperature (10 ℃) | |||||
| Kind | X (weight %) | Kind | Y (weight %) | Standard test (I) | Standard test (II) | Time of arrival (second) | Hydraulicity slip viscosity (20 ℃) | Time of arrival (second) | Hydraulicity slip viscosity (10 ℃) | ||
| 5-1 | Pentanedioic acid | 10.0 | Capric acid | 0.00 | 130mPa·s | Have | Have | 7 | 6300mPa·s | 30 | 4500mPa·s |
| Nonane diacid | 1.0 | ||||||||||
| 5-2 | Pentanedioic acid | 10.0 | Capric acid | 1.00 | 235mPa·s | Have | Have | 5 | 6300mPa·s | 7 | 4500mPa·s |
| Nonane diacid | 1.0 | ||||||||||
Claims (12)
1. liquid rheology modifier, it contains the 1st water-soluble low-molecular compound (hereinafter referred to as compound (A)), 2nd water-soluble low-molecular compound (hereinafter referred to as compound (B)) and the dicarboxylic acid (C) different with compound (A), wherein, the combination of compound (A) and compound (B) is selected from following combination: (1) is selected from the compound (A) of cationic surfactant and is selected from the combination of the compound (B) of anionic property aromatics, (2) be selected from the compound (A) of cationic surfactant and be selected from the combination of the compound (B) of brominated compound.
2. the described liquid rheology modifier of claim 1, wherein, the content of dicarboxylic acid (C) in liquid rheology modifier is 0.1～30 weight %.
3. claim 1 or 2 described liquid rheology modifiers wherein, are stopping to can be observed when stirring circling round of bubble in the solution in following standard test (I),
Standard test (I): adding 0.1N potassium hydroxide aqueous solution 90mL, rheology modifier 10mL in the 200mL beaker, is that the glass stick of 6mm stirred for 180 seconds with the speed of 4 circle/seconds with diameter then.
4. claim 1 or 2 described liquid rheology modifiers wherein, are stopping to can be observed when stirring circling round of bubble in the solution in following standard test (II),
Standard test (II): adding 0.1N potassium hydroxide aqueous solution 95mL, rheology modifier 5mL in the 200mL beaker, is that the glass stick of 6mm stirred for 180 seconds with the speed of 4 circle/seconds with diameter then.
5. claim 1 or 2 described liquid rheology modifiers, it further contains monocarboxylic acid (E).
6. liquid rheology modifier, it contains the 1st water-soluble low-molecular compound (hereinafter referred to as compound (A)), the 2nd water-soluble low-molecular compound (hereinafter referred to as compound (B)) different with compound (A) and the amphiphilic compound (D) with hydrophilic group and hydrophobic group except that compound (A) and compound (B), wherein, the viscosity of described properties-correcting agent under 20 ℃ is below the 5000mPas; The combination of compound (A) and compound (B) is selected from following combination: (1) is selected from the compound (A) of cationic surfactant and the combination of the compound (B) that is selected from the combination of the compound (B) of anionic property aromatics, compound (A) that (2) are selected from cationic surfactant and is selected from brominated compound; In following standard test (I), when stopping to stir, can be observed circling round of bubble in the solution,
Standard test (I): adding 0.1N potassium hydroxide aqueous solution 90mL, rheology modifier 10mL in the beaker of 200mL, is that the glass stick of 6mm stirred for 180 seconds with the speed of 4 circle/seconds with diameter then.
7. liquid rheology modifier, it contains the 1st water-soluble low-molecular compound (hereinafter referred to as compound (A)), the 2nd water-soluble low-molecular compound (hereinafter referred to as compound (B)) different with compound (A), and dicarboxylic acid (C), wherein, the combination of compound (A) and compound (B) is selected from following combination: (1) is selected from the compound (A) of cationic surfactant and is selected from the combination of the compound (B) of anionic property aromatics, (2) be selected from the compound (A) of cationic surfactant and be selected from the combination of the compound (B) of brominated compound; The viscosity of described liquid rheology modifier under 20 ℃ is below the 5000mPas; In by normal portland cement 400g and the synthetic slip of water 400g, add described liquid rheology modifier 16g and mix, just carried out mixed slip viscosity at 20 ℃ down for more than the 3000mPas.
8. the described liquid rheology modifier of claim 7 wherein, in following standard test (II), can be observed circling round of bubble in the solution when stopping to stir,
Standard test (II): adding 0.1N potassium hydroxide aqueous solution 95mL, rheology modifier 5mL in the 200mL beaker, is that the glass stick of 6mm stirred for 180 seconds with the speed of 4 circle/seconds with diameter then.
9. claim 7 or 8 described liquid rheology modifiers, it further contains monocarboxylic acid (E).
10. slip, it contains each described liquid rheology modifier in powder, water and the claim 1,2,6,7 and 8.
11. a slip, it contains each described liquid rheology modifier in hydraulic powder, water and the claim 1,2,6,7 and 8.
12. each described liquid rheology modifier is used for the pulp flow sex change is carried out the purposes of modification in the claim 1,2,6,7 and 8.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP241344/2006 | 2006-09-06 | ||
| JP2006241344 | 2006-09-06 | ||
| JP2007101577 | 2007-04-09 | ||
| JP101577/2007 | 2007-04-09 |
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| CN101144001A true CN101144001A (en) | 2008-03-19 |
| CN101144001B CN101144001B (en) | 2012-10-10 |
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|---|---|---|---|
| CN2007101472870A Active CN101144001B (en) | 2006-09-06 | 2007-09-06 | Liquid rheology modifier |
Country Status (6)
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| US (1) | US8648120B2 (en) |
| EP (1) | EP1897927A3 (en) |
| JP (1) | JP5362200B2 (en) |
| KR (1) | KR101390409B1 (en) |
| CN (1) | CN101144001B (en) |
| TW (1) | TWI424976B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115925447A (en) * | 2022-12-29 | 2023-04-07 | 东南大学 | Modifier with wettability responding to pH and using method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| AU2009291163B2 (en) * | 2008-09-10 | 2014-04-24 | Construction Research & Technology Gmbh | Use of cyclohexane polycarboxylic acid derivatives for removing dust from chemical construction products |
| JP5476082B2 (en) * | 2009-09-30 | 2014-04-23 | 花王株式会社 | Liquid rheology modifier |
| JP2012031277A (en) * | 2010-07-30 | 2012-02-16 | Kao Corp | Method of producing liquid rheology modifier |
| US20150152008A1 (en) * | 2012-05-29 | 2015-06-04 | Construction Research & Technology Gmbh | Pulverulent accelerator |
| EP3233751B1 (en) | 2014-12-18 | 2019-03-13 | Basf Se | Construction chemical composition for tile mortar |
| EP3568381A4 (en) | 2017-01-15 | 2021-06-09 | Butler, Michael, George | Apparatuses and systems for and methods of generating and placing zero-slump-pumpable concrete |
| US20200284277A1 (en) * | 2019-03-05 | 2020-09-10 | Ohio State Innovation Foundation | Drag Reducing Agents and Methods of Using Thereof |
| JP7488118B2 (en) | 2020-06-05 | 2024-05-21 | 花王株式会社 | Liquid Rheology Modifiers |
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|---|---|---|---|---|
| SE8604714L (en) * | 1985-11-15 | 1987-05-16 | Colgate Palmolive Co | DETERGENT COMPOSITION WITH IMPROVED ABILITY TO REMOVE OILY DIRT |
| US4721580A (en) * | 1987-01-07 | 1988-01-26 | The Procter & Gamble Company | Anionic end-capped oligomeric esters as soil release agents in detergent compositions |
| US5672578A (en) * | 1994-02-03 | 1997-09-30 | The Procter & Gamble Company | Limescale removing compositions |
| EP0875552A1 (en) * | 1997-04-30 | 1998-11-04 | The Procter & Gamble Company | Acidic limescale removal compositions |
| US6239183B1 (en) * | 1997-12-19 | 2001-05-29 | Akzo Nobel Nv | Method for controlling the rheology of an aqueous fluid and gelling agent therefor |
| EP1212385B1 (en) * | 1999-09-07 | 2015-12-30 | Akzo Nobel Surface Chemistry Aktiebolag | Quaternary ammonium salts as thickening agents for aqueous systems |
| US6371174B1 (en) | 2001-01-25 | 2002-04-16 | Illinois Tool Works, Inc. | Adhesive application system and method of use |
| EP1266875A3 (en) * | 2001-06-15 | 2009-10-21 | Kao Corporation | Slurry rheology modifier |
| JP3875137B2 (en) | 2001-06-15 | 2007-01-31 | 花王株式会社 | Slurry rheology modifier |
| JP4216061B2 (en) | 2002-12-13 | 2009-01-28 | 花王株式会社 | Rheology modifier kit |
| JP4318976B2 (en) | 2003-07-15 | 2009-08-26 | 大日本印刷株式会社 | Inkjet printer printing alignment device |
| JP4503403B2 (en) * | 2003-10-07 | 2010-07-14 | 花王株式会社 | Rheology modifier |
| US7846876B2 (en) * | 2003-10-07 | 2010-12-07 | Kao Corporation | Surfactant composition |
| US7595284B2 (en) * | 2004-06-07 | 2009-09-29 | Crews James B | Metal-mediated viscosity reduction of fluids gelled with viscoelastic surfactants |
| JP4832845B2 (en) | 2005-10-04 | 2011-12-07 | 花王株式会社 | Slurry production method |
| ES2614648T3 (en) * | 2007-04-06 | 2017-06-01 | Kao Corporation | Procedure to produce dust |
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2007
- 2007-09-04 TW TW096132922A patent/TWI424976B/en active
- 2007-09-05 EP EP07017354.7A patent/EP1897927A3/en not_active Withdrawn
- 2007-09-05 JP JP2007230199A patent/JP5362200B2/en active Active
- 2007-09-05 US US11/896,760 patent/US8648120B2/en active Active
- 2007-09-06 CN CN2007101472870A patent/CN101144001B/en active Active
- 2007-09-06 KR KR1020070090496A patent/KR101390409B1/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115925447A (en) * | 2022-12-29 | 2023-04-07 | 东南大学 | Modifier with wettability responding to pH and using method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| US8648120B2 (en) | 2014-02-11 |
| EP1897927A2 (en) | 2008-03-12 |
| KR20080022532A (en) | 2008-03-11 |
| KR101390409B1 (en) | 2014-04-29 |
| US20080078814A1 (en) | 2008-04-03 |
| EP1897927A3 (en) | 2015-08-12 |
| JP5362200B2 (en) | 2013-12-11 |
| JP2008280502A (en) | 2008-11-20 |
| CN101144001B (en) | 2012-10-10 |
| TWI424976B (en) | 2014-02-01 |
| TW200823160A (en) | 2008-06-01 |
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